AU739878B2

AU739878B2 - Starch/cationic polymer combinations as coagulants for the mining industry

Info

Publication number: AU739878B2
Application number: AU87153/98A
Authority: AU
Inventors: Jeffrey A Jankowski; Calvin T Tobinson
Original assignee: Nalco Chemical Co
Current assignee: ChampionX LLC
Priority date: 1997-09-29
Filing date: 1998-09-29
Publication date: 2001-10-25
Anticipated expiration: 2018-09-29
Also published as: AU8715398A; CA2248479A1; EP0905091A1; US6042732A; ZA988880B

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): NALCO CHEMICAL COMPANY Invention Title: STARCH/CATIONIC POLYMER COMBINATIONS AS COAGULANTS FOR THE MINING INDUSTRY The following statement is a full description of this invention, including the best method of performing it known to me/us:

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Field of the Invention A method for dewatering coal tailings, clean coal products and mineral slurries with an effective coagulating amount of a combination of a cationic polymer and a starch.

A preferred cationic polymer is poly(dimethylaminoethylacrylate methyl chloride quaternary salt) and preferred starches are unmodified.

ackground of the Invention Coal is the most abundant natural energy source in the world. A significant portion of the U.S. domestic energy requirements are met by burning coal as a fossil fuel.

There are various types of coal found within the anthracite, semi-anthracite, S 10 low-volatile bituminous coal, medium- and high-volatile bituminous coal, subbituminous coal, and lignite. Coals such as anthracite and semi-anthracite typically have high ash and sulfur contents and therefore require beneficiation prior to use.

The primary purpose of coal beneficiation is to reduce the incombustible ash content. thus enhancing the heat content. Reduction in the ash content results in savings 15 in transportation and ash disposal costs. Sulfur, mainly in the form of purite, is also reduced.

Another important economic factor to be considered in coal processing is the recovery and reuse of process water. Water is typically very expensive and there are often limits on total usage. Also. strict environmental controls prohibit or severely limit discharge of process water. Thus, it is imperative that solids be efficiently removed from the process water and water recycled to the process stream.

Beneficiation of coal is effected using two primary properties of coal, (1) differences in specific gravity between coal and its impurities, and differences in 10 surface characteristics between coal and its impurities. Since the higher ash content fractions are usually found in the finer coal sizes, some plants only screen out these sizes to beneficiate the coal. However, since the quantity of such fine coal is on the rise, even this is treated.

A coal beneficiation plant may be broadly divided into specific gravity separation and fine coal treatment. In gravity separation, cleaning units make use of the differences in specific gravity between coal and its impurities to effect separation. Normally, the specific gravity of the clean coal is less than that of its impurities. Some examples of commonly used equipment for gravity separation are: jigs, heavy medium baths and cyclones, washing tables, water-only cyclones and spirals.

Fine coal treatment incorporates a flotation cell(s), clean coal filter and thickener.

In the flotation cell, a collector and frother are added to the flotation feed. A collector such as diesel oil selectively imparts hydrophobicity to the coal particles. This increased hydrophobicity makes the air bubbles more likely to attach to the coal particles. The frother. generally an alcohol-based product, reduces the surface tension of the air/water interface, thus making a stable froth.

The clean coal concentrate from the flotation cells goes to the clean coal filter and is dewatered. The tailings from the flotation cell go to the thickener where they are thickened and discharged.

The thickener is treated with coagulants and flocculants to enhance settling.

Typically. the coagulants and flocculants are added at several points along the feed line to the thickener and in different sequences. Coagulation is the destabilization by surface charge neutralization of stable negatively charged particles that are in suspension settlcable or dispersed) through the utilization of inorganic salts or cationic -3- 0 0. 0 0* 0 0..

15 polyelectrolytes. Flocculation is the aggregation of finely divided particles which are suspended in a liquid through the utilization of an enirapping agent, generally an inorganic flocculant, or a bonding agent, generally an organic flocculant, that brings the particles together, During the processing of coal, a coal refuse slurry is generated. This slurry consists of residual coal fines and clays suspended in plant process water. Due to the high volume of water used in the processing of coal, it is necessary to reclaim the wash water for recirculation in the plant. The concentrated solids are sent to an impoundment pond for disposal. Generally, the use of anionic flocculants is sufficient to remove the majority of the coal fines; however, when there are high levels of clay in the mined coal, it is necessary to supplement the use of anionic flocculants with the use of cationic coagulants. The sequential addition of flocculants and coagulants is used primarily in the coal refuse thickener and in the subsequent twin belt press filtration of the thickener underflow. The typical application order in the thickener, which is similar to a clarifier, is coagulant addition followed by flocculant addition, This provides a controlled turbidity of the recycle process water and a controlled solids settling rate. In the thickener underflow filtration, the order of application is normally flocculant followed by coagulant. This treatment gives highly agglomerated solids which provides effective dewatering of the Waste solids and low turbidity in the recycled process water, The decrease in sludge volume or the increase in sludge solids results in more efficient use of plant process water and a reduced loading in the impoundment pond. The impoundment pond is the area of the mine where the sludge is used to landfill existing mined surfaces. With time, the sludge further compresses in the impoundment area which provides reclaimed mine sites.

The typical equipment used for sludge thickening and dewatering in the coal industry are Gravity Thickeners, Twin Belt Presses, and Rotary Drum Filters. Each of these pieces of equipment uses flocculants and coagulants. The doses of flocculant and cationic polymers are 5 10 ppm and 1 5 ppm, respectively, for the thickener and 5 ppm and 5 30 ppm, respectively, for the filter applications. These polymers are highly surface active and they remain with the solids that are sent to the impoundment pond.

These products are used in closed loop coal refuse treatment applications. A treating polymer is also required for the dewatering of other mining underflow solids such as copper ore refuse slurries.

10 In addition to the treatment of fine coals, dewatering is also necessary in other areas of mineral processing. A variety of mineral slurries such as taconite, trona, sand and gravel slurries and titania require solids removal and dewatering. The same basic processing steps are utilized to extract titanium oxide from titania, for example.

Although some inorganics, principally alum and iron salts, are still used as 15 -coagulants, water soluble organic polymers are now more prevalent. Both naturally occurring and synthetic polymers find use as coagulants and flocculants in the mining industry. The principal natural polymers used are starch and guar, both of which are i high-molecular weight polymers of simple sugars, such as polysaccharides. Starch is a polymer of glucose consisting of a mixture of linear (amylose) and branched segments (amylopectin).

Synthetic polymers are advantageous because they can be tailored to a specific application. This has resulted in a wide range of commercially available coagulants and flocculants of varying charge, composition, and molecular weight. The most widely used synthetic coagulants are polydiallyldimethylammonium chloride (polyDADMAC) having molecular weights in the range of from 100,000 to as high as 1,000,000 or higher and condensation polymers of dimethylamine and epichlorohydrin (Epi/DMA) which generally have molecular weights in the range of 20,000 to 100,000.

The most widely used synthetic coagulants are polydiallyldimethyl ammonium chloride as described in U.S. 2,926,161 and condensation polymers of dimethylamine and epichlorohydrin such as those described in U.S. Reissue Patents 28,807 and 28,808, though co-polymers of 3-acrylamido-3-rnethylbutanoic acid and acrylamide or acrylic acid are also known, as described in U.S. Patent No. 5,296,006. These polymers vary 10 greatly in molecular weight, typically ranging from several thousand to as high as 500.000. Condensation polymers are made in solution form, and are available S. commercially as aqueous solutions containing a relatively low weight peicent polymer.

Polydiallyldimethyl ammonium chloride is a vinyl addition polymer, which (at the molecular weights used for coagulation) has also been made in solution form, Typical commercially available polydiallyldimethyl ammonium chloride is available in aqueous oo*.* solutions containing 1-20% by weight polymer.

Copolymers of diallyldimethylammonium chloride and acrylamide having utility •for the dewatering of mineral slurries have been described in U. S. Patent No. 4,673,511.

I ffective co-polymers consisting of co-polymerizing diallyldimethylammonium chloride 21 (DADMAC) with various other monomers are also known. For example, U.S. Patent No.

5.330.546 discloses effective co-polymers of DADMAC with a dialkylaminoethylacrylate or a dialkylaminoethylmethacrylate; U.S. Patent No, 5,476,522 discloses effective copolymers of DADMAC with a vinylalkoxysilane; U. S. Patent No. 5,653,886 discloses tcrpolvmers formed from polymerization of monomers including DADMAC and U.S.

-6- 10 1 a. Patent No. 5,518,634 discloses polymers formed from DADMAC and acrylamide, crosslinked with triallylamine.

Copolymers of DMAEA.MCQ (dimethylaminoethylacrylate methyl chloride quaternary salt) and acrylamide have been described as floccilants in U.S. Patent No.

4,720,346. Copolymers of DMAE(M).MCQ and DADMAC as treatment materials are described in U.S. Patent No. 4,835,206.

Dry water soluble polymers such as dry polydiallyldimethyl ammonium chloride have also been used to dewater coal refuse slurries. These polymers have met with some success, dissolving in the refuse thickener over a period of 45 to 60 seconds. Such time is long enough to provide continuous feed of fresh polymer into the coal/clay slurry.

Homopolymers in solution or solid form produced by polymerizing dialkylamonoalkyl(meth) acrylates quatemized by methyl chloride improving the stability of coal dispersions and assisting the separation of coal from mineral matter are described in U.S. Patent No. 4,370,429. Moreover, dry homopolymers formed from dialkylaminoalkyl(meth)acrylamides as quaternary ammonium salts have been disclosed in U.S. Patent No. 5.178,774. That reference also teaches that some starch may be utilized as a carrier to promote formation of particles with the cationic polymer. Yet that reference teaches that for best efficiency, starch should not be used, and therefore contradicts the findings described herein.

Starch is described as a dehydrating agent for a coal froth in Kokai No. 59- 122594. However, combinations of starch and polymer are not indicated in this reference, and as will be demonstrated by the disclosed examples, the combination of polymer with starch results in an unexpectedly large increase in performance.

Therefore, since there is still a need to achieve better performance, leading to better clarity, reduced consumption of polymer, or simpler operation, the use of polymer/starch combinations as described herein is desirable as they result in improved efficiency of processes in the mining industry.

Summary of the Invention A method for dewatering coal tailings, clean coal products and mineral slurries with an effective coagulating amount of a combination of a cationic polymer and a starch.

A preferred cationic polymer is poly(dimethylaminoethylacrylate methyl chloride 10 quaternary salt) and preferred starches are unmodified.

Description of the Invention One aspect of this invention is a method for dewatering coal tailings containing water. said method comprising the steps of: 1 a. feeding said coal tailings to a thickener; b. contacting said coal tailings with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; c. allowing said coal tailings to settle to the bottom of the thickener to obtain concentrated coal tailings; 0 d. discharging said concentrated tailings from said thickener; and e. withdrawing clarified liquid from said thickener.

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15 The following information is applicable to any aspect of the inivention described herein. The method may further comprise the addition of a flocculant. Moreover, the flocculapt may be a copolymner of acrylamride and acrylic ac id. The thickener may be a gravity sedimentation device. The polymer may be a dry Polymer formed from polymerization of one or more monomers selected from the group consisting of dimethylaminoethylacrylate methyl chloride quateinary salt, acrylamide, d imethylamninoethylacrylate benzyl chloride quaternary salt, dimethylarninoethylmethacrylate methyl chloride quaternary salt, dirnethylaminoethylmethyacryl ate benizyl chloride quaternary salt, diallyldimethylammoniumn chloride and combinations thereof. Alternatively, the polymer may be a solution polymer formed fromn polymerization of one or more monomers selected from the group consisting of dirnethylaminoethylacrylate methyl chloride quaternary salt, dirnethylaminoeihylacrylate benzyl chloride quaternary salt, d imethyl am inoethylImethacry late methyl chloride quaternary salt, d imethylaminoethy I methyacry late bentzyl chloride quaternary salt, diallyldimethylammonium chloride and combinations thereof. The polymer may be an e.piciorohydrin/dimethylamirie polymer or a polyamine formed from reaction of ethylene dichloride and ammonia. The Starch may be selected from the group consisting of unmodified starch, pregelatinized starch. hydrolyzed starch and combinations thereof.

The polymer/starch combination may be at least 30 weight percent starch. A specific combination is where the polymer is poly(dimethylaminoethylacrylate methyl chloride quatcrrary salt) and the starch is unmodified starch; wherein the ratio of polymer to starch in said combination is from about 70:30 to about 20:80. Preferably, the ratio of polymer to starch in said combination is from about 60:40 to about 25:75. More -9- ,0 I f. preferably, the ratio of polymer to starch in said combination is from about 50:50 to about 35:65.

Another aspect of the invention is a method for dewatering a clean coal product containing water comprising the steps of: a. feeding a clean coal product containing water to a mechanical filtering device; b. contacting said clean coal product with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; c. removing water from said clean coal product; and then, d. recovering a dewatered clean coal product from the mechanical filtering device. For the practice of this invention, the mechanical filtering device may be selected from the group consisting of gravity thickeners, twin belt presses and rotary drum filters.

Yet another aspect of this invention is a method for dewatering mineral slurries containing water comprising the steps of: a. feeding the mineral slurry into a thickener; b. treating said mineral slurry with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; c. allowing the water to separate from the mineral slurry; d. withdrawing water from said thickener; and e. discharging the dewatered mineral products from said thickener.

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S 1 For the practice of this aspect of the invention, the mineral slurry-rmay be selected from the group consisting of: titania, copper, trona, beryllium and taconite slurries.

Another aspect of this invention is a method for clarifying the water contained in a coal refuse slurry, said method comprising the steps of: a. treating the coal refuse slurry with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; b. allowing the water to separate from the coal refuse; c. feeding the separated water and coal refuse into a twin belt filter press; d. withdrawing the clarified water through the twin belt filter press; and e. removing the coal refuse from the twin belt filter press.

The DMAEA.MCQ and DADMAC polymer solutions can have an intrinsic viscosity of from about 0.2 to about 5 dL/g as determined in 1-M sodium nitrate at 30 *C, 1 weight-percent solution. However, low molecular weight polymers are preferred for ease of pumping as a solution and for rate of dissolution when used as a dry product. The DMAEA.MCQ polymers have a preferred intrinsic viscosity of from about 0.1 to about dL/g and more preferable from about 0.3 to 1.0 dL/g.

The DMAEA.MCQ polymers can be prepared by conventional means known in the art including latex emulsion, solution, suspension or bulk polymerization techniques.

Aqueous solutions of the polymer are preferably prepared as described in Example 1.

Concentration of monomer in the reaction mixture will typically range from about 10 to 11

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10 i about 40 percent by weight of the reaction mixture to produce the aqueous solution polymer having a polymer actives concentration between 10-40 percent by weight of the solution.

The starch products that are used may be unmodified, physically modified (e.g.

pregelatinized), or chemically modified cross-linked, substituted, hydrolyzed).

However, higher molecular-weight, unmodified, low-charge starches are preferred because of the activity they provide. The starch may be dry or in solution, If the cationic polymer and starch are to be used as solutions they can be made and dosed as a blend or as separate solutions; however, it is preferable to make and dose them as separate solutions. Solution concentrations can be up to about 60% depending on the molecular weight of the cationic polymer and the type of starch used, and the ratio of cationic polymer to starch polymer. For dosage to the system to be treated, the solutions should be diluted to from about 0.01% to about 2% total actives. If made up separately, the starch and cationic polymer solutions can be dosed at the same time or in two or more increments and in different orders of addition, It is preferable to use a split addition of the cationic and starch polymers with the cationic polymer being added first.

If the cationic and starch polymers are to be converted to a dry material for use, the two products may be blended together in a single solution in concentrations from about 10 to about 60% depending on the viscosity as determined by the molecular weight of the polymers, the type of starch used, and the ratio of cationic polymer to starch 12- 1 polymer. The ratio of cationic polymer:starch polymer in the final dry product can range from about 70:30 to about 20:80. A preferred range of ratios if from about 60:40 to about 25:75 and a more preferable range from about 50:50 to about 35:65. The solution may then be dried by conventional means known in the ar such as tray drying, spray drying or drum drying. The material must be ground for ease of handling and addition to the system, The particle size-can range from about 10 mesh (2.0 mm) to about 400 mesh (38 ipmi. A preferable particle size range is from about 18 mesh (1.0 mm) to 200 mesh (125 im) with a more preferable range from 40 mesh (425 pm) to 100 mesh (150 pm).

The polymers and copolymers of this invention may be used alone, or in 10 combination with a high molecular weight anionic or non-ionic water-soluble or dispersible flocculant. Such polymers include polyacrylamide, and copolymers of acrylamide with acrylic acid and its water-soluble alkali metal or ammonium salts. Also useful are such polymers as sufomethylated acrylamides as exemplified in U. S. Patent Nos. 5.120.797 and 4,801,388, the disclosures of which are hereinafter incorporated by 15 reference into the specification. Other commercially available anionic flocculant materials may also be utilized.

A preferred class of flocculants for use in this invention includes copolymers of acrylamide and acrylic acid having a mole ratio of acrylamide to acrylic acid of from 99:1 to 1:99 and preferable 99:1 to 50:50. Most preferably, the mole ratio of acrylamide to -13l acrylic acid will be 95:5 to 60:40. An especially preferred flocculant foi"se in this invention has a mole ratio of acrylamide to acrylic acid of about 70:30.

The flocculants of this invention may be prepared in solution form, or in water-inoil emulsion form. The preparation of such flocculants is known to those skilled in the art. The flocculants generally have molecular weights ranging from as low as 1,000,000 to 20,000,000 or higher. Preferred flocculants have a molecular weight of about 10,000,000. The upper weight of molecular weight is not critical so long as the polymer is water soluble or dispersible.

The flocculant is believed to cause the aggregation of the neutralized colloidal particles which are suspended in the tailings suspension. Aggregation is the result of either entrapping agents inorganic flocculants) or bonding agents organic flocculants) bringing the neutralized particles together.

The coagulants and flocculants can be added at several points along the feed line to the thickener and in different sequences. The flocculants may be added either prior to or subsequent to coagulant addition. A typical thickener is a gravity sedimentation unit which is a cylindrical continuous thickener with mechanical sludge raking arms. The tailings a solids/liquid dispersion) enter the thickener at the centerwell. The coagulants and/or flocculants are added at points in the feed line and/or centerwell. The number of addition points, sequence, flocculant, coagulant, etc. are determined by laboratory cylinder tests for each particular application. The flocculated solids settle to -14-

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the bottom of the thickener. The mechanical arms rake the sludge and itis-discharged.

The clarified water overflows into a launder surrounding the upper part of the thickener.

The cationic polymer/starch blends may be added to the thickener or mechanical filter device at a rate of about 0.001 to about 0.3 Ib/ton of slurry, and preferably 0.005 to about 0.25 Ib/ton. Most preferably from about 0.01 to 0.25 of polymer is used per ton of slurry. The-amount of coagulant will vary according to the particular stream to be dewatered, and whether the coagulant is added as a solution or as a dry material.

Flocculant may also be added to the thickener in an effective amount, generally between about 0.01 to about 0.25 Ib/ton of slurry.

After treatment of the slurry with sufficient coagulant and optional flocculant, the thickener underflow or refuse concentrated tailings) are removed from the bottom of the thickener, while water and/or other liquids are taken out overhead. The water can thereafter be recycled as process water for use in the benefication process or disposed of in impoundment ponds. The concentrated railings or refuse from the thickener can be thereafter disposed of.

In most instances, adding a given amount offlocculant in two or more increments results in better performance than adding the same amount of flocculant in one increment.

It is not unusual to be able to reduce the amount of flocculant required by as much as by multi-point addition and still achieve the required settling rate. Multi-point 0e S.

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This practice is implemented in a benefication plant process by adding the flocculant at different points in the feed line to the thickener. The improvement results from reducing the amount of surface area that the second or third portion of flocculant actually conitacts when added to the system, as well as improved distribution of the flocculant.

The use of combinations of polymer and starch as coagulants also has a broader applicability to the concentration of aqueous suspensions of inorganic solids in general.

Among the inorganic solids which may be processed inthis manner are gravel, sand and kaolin. The combination may have applicability to the dewatering of natural or other industrial waters.

Additionally, the use of combinations of polymer and starch as described herein may have a positive effect on improvement of retention and drainage in pulp and paper applications.

The following examples are presented to describe preferred embodiments and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims appended hereto.

-16- Example 1 For a lab-scale reaction, a 40% actives aqueous solution of a low molecular weight DMAEA.MCQ polymer was prepared in a 1.5-L batch reactor with a stirrer, thermocouple, reflux condenser, and nitrogen purge. 500 g (50.000 wr%) of DMAEA.MCQ (available from NCF Manufacturing of Riceboro, GA) monomer (as an solution in water) wasdissolved in 495.25 g of deionized water (49.525 along with 075 g (0.075 wt%) sodium hypophosphite to control the molecular weight of the polymer and mixed in the reactor. The solution was purged with Nz and warmed to 40 °C over 30 minutes. At that time, 4.00 g of a V-50 solution (2,2'-azobisisobutyronitrile available from DuPont Specialty Chemicals, Inc. of Wilmington, DE) (10% in water), is added to initiate the polymerization. The polymerization begins within 3-10 minutes. No attempt is made to cool the reaction. After the reaction reaches its maximum temperature, 78 OC, it is held at that temperature for 30 minutes. The reactor was cooled to room temperature and the contents were transferred to a container for 15 evaluation. The product was characterized by measurement of an intrinsic viscosity (IV) (1M NaNO 3 solution. 1 wt% polymer solutions), colloidal titration (0.0025 g product against 0.0002 N potassium salt of polyvinyl sulfuric acid (PVSK)), and residual monomer concentration. The polymer samples used for the experiments presented in this patent were from a 100-gallon direct scale-up of the aforementioned reaction.

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For each DMAEA.MCQ;starch ratio to be tested, aqueous solutions containing total actives of the desired blend were prepared by blending the appropriate amount ,of water and starch into the 40% DMAEA.MCQ solution polymer described above. For testing as a liquid coagulant, the solutions were diluted to 1% total actives and tested. To produce the dry coagulant samples, the 40% solutions were dried in shallow aluminum pans in a 100-105 *C oven for no more than 4 hours. After cooling, the samples were grounrd in small batches for 15 seconds in a 8-oz. blending container using a standard kitchen blender set to "grind." Dry material that would pass through a 20 mesh screen was collected and used for testing.

Cylinder settling tests using coal refuse slurry were used to quantitate the activity of the coagulant products and their affect on flocculant activity in the same system. A 5-gallon bucket of slurry was allowed to mix while 1-L glass graduated cylinders were filled 500-mL at a time until random sampling was completed. Masking tape was placed on each cylinder, aligned along the cylinder graduation test marks For each test, a cylinder was inverted several times to suspend any settled solids. The cylinder was then dosed with the coagulant to be tested (solution coagulants were added via syringe, dry coagulants were quantitatively transferred from a plastic weigh boat), and inverted four times. Quickly, the cylinder was then dosed with a 0.1% solution of a flocculant (moderately anionic acrylamide/acrylate copolymer) and inverted four more times. This step was then performed a second time, dosing with the same amount of 0.1% flocculant -18and inverted four more times for a total of 3 additions of chemical treatment and 12 inversions. After the last inversion, when the cylinder was returned to the upright position, a timer was started and the position of the solids interface was monitored as a function of time, with marks being made on the masking tape at appropriate intervals. At the point of hindered settling, when the rate of descent of the interface starts to slow down, marking was terminated. The settling rate, in inches/minute, for the free-fall regionxtf settling was calculated for each test. For turbidity measurements, a sample of water above the settled solids was taken from the top portion of the cylinder 3 i minutes after timing for the settling rate was initiated. Turbidity readings in NTUs were obtained using a Hach 2100P Turbidimeter. A decrease in NTU value indicates an increase in efficiency for this application.

The results in Table I illustrate the superior performance of a dry coagulant over that of a solution coagulant of the same actives composition. For dry DMAEA.MCQ and dry DMAEA.MCQ/starch (pregelatinized starch, DRILSTAR EW, Chemstar Products, 15 co.) blends (containing from 100 to approximately 60% DMAEA,MCQ), twelve times as much active polymer must be added in the solution form to achieve the same clarity as that obtained with the dry form.

The results in Table I also reveal that the amount of cationic polymer, in either solution or dry form of the coagulant, can be replaced with up to 40% starch by weight to achieve the same level of clarity. This demonstrates a significant synergy between the -19starch and the cationic polymer in reducing turbidity because starch by itself is ineffective as a coagulant (see Example 2.) TABLE I Resulting Turbidity (NWU) with poly(D)MAEA.MCQ)/Starch Blends Dry Products vs. 11/ Solutions dry dry -poly 1% Solution 1% Solution Cationic poly(DADM4AC)' (DMAEAMCQ) 2 poly(M MC) poly(DMAEAMCQ)Y Polymer (5 ppm) Starch 3 (5 ppm) S=ach (s ppm) Starch 3 (60 ppmn) 100 172 155 2700 101 so 201 2600 227 60 385 2700 331 40 2400 3200 1() 15

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2() =available from Nalco Chemical Co. of Naperville, IL 2=available from Nalco Chemical Co. of Naperville, I 3 =DRILSTAR EW (pregelatinized corn starch) available from Chemstar Products Co. of Minneapolis,

MN

The procedure described in Example I was utilized to obtain the results of Tables 11, 111. and IV. The dry poly(DADMAC) and poly(DADM4AC)/starch combinations were derived from a solution DADMAC polymer, in the same manner as the dry DMAEA.MCQ and DMAEA.MCQ/statch polymers described in Example I.

In the case of both poly(DADMAC) (Tables 11 and IV) and poly(DMAEA.MCQ) (Tables IIl and IV) pregelatinized starch (DRILSTAR EW, Chernstar Products, Co.) was used io displace the cationic polymer, and the turbidity values achieved with the blends 20 containing up to 60% starch were comparable to those achieved for the cationic polymer alone. In addition, the turbidity values obtained with the cationic polymer/starch blends were significantly below those that would be expected for a direct replacement in activity between the cationic polymers and the starch indicating a synergistic effect between the two compounds- TABLE II Effect of Starch on the Performance of poly(DADMAC)' as a Coagulant in Dry Form .p .Siarch' oyDDA~ 0 29.4 7. 2 38.5 41 5 7 45.5 55.6 44.4 100 0 )000 I=available from Nalco Chemical Co. of Naperville, IL 3 -DRILSTAR EW (pregelatiriized corn starch) available ffrm Chemstar Products Co. of Minneapolis,

MN

-21 TABLE mR Effect of St arch on the Performance of poly(DMAE-A.MCQ) 2 as a Coagulant in Dry Forin 0O 10 51 22. 70. 25.0~ fo ac Ceia C.o aeril, S=D LSA EW peeltfidcontrh)available fromNlc Chemstacaodct Co. of Mapervaloes,

MN

TABLE IV Resulting Turbidity (NYU) of Cationic Polymers with Starch as Coagulants in Dry Form 5 a S.

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s0 ODGI 1 00 0 4930 4930 available from Nalco Chemical Co. of Naperville, IL 2 available from Nalca Chemical Co. of Naperville, IL 3 DRILSTAR EW (pregelatinized corn starch) available from ChemsTar Products Co. of Minneapolis,

MN

The procedure described in Examiple I was utilized to obtain the results of Table V. For these experiments, 500-rnL cylinders were used and the starch and 22- Is poly(DMAE-A.MCQ) solutions were 0.2% actives. Total coagulant dosage-was 24 ppm, except in the case of the poly(DMAEA.MCQ) added alone. These results demonstr~ate the affinity that starch and poly(DMAEA.MCQ) have for each other in solution and how this affinity can negate the synergistic effect if the starch/coagulant blend is made up and dosed as a single solution.

For example, dosing-a blend of 80% poly(DMAEA.MCQ)/20% pregelatinized starc"- DRILSTAR EW) gave a turbidity of almost 1200 NTU, whereas just dosing the actives equivalent of the poly(DMIAEA.MCQ) 19.2 ppm (80% of 24 ppm) gave an NTtJ value below 300. Adding the 19.2 ppm acfives as poly(DMAEA.MCQ) and the complementary 4.8 ppm actives as starch at the same time but as separate solutions gave an NTU value slightly above 150. The turbidity values increased dramatically with a decrease in the dosage of poly(DMAEA.MCQ) by itself. This decline was definitely abated by concurrently adding a complementary amount of starch to maintain the total actives at 24 ppm.

23 TABLE V Resulting Turbidity (NMIJ of poly(DMAEA.MCQ) with Starch as a Coagulant in Solution Form Treatments poly(DMAEA.MCQ)' poly(DMAEA.MCQ) 2 poly(DMAEA.MCQ) 2 and Starch' added Starch 3 Polymer only- Starch 3 bland concurrentily 0 100 115 115 115 80 279 1196 157 60 -1116 1429 324 40 1808 527 8W 20 964 100 0 2058 5 10

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*5 S 2 available from Nalco Chemical Co. of Naperville, IL 3 =DRILSTAR EW (pregelatinized corn smtch) available ftrm Chernsta Products Co. of Minneapolis,

MN

ExampleA The procedures described in Examples I and 3 were used to obtain the results in Table VI. In these experiments the solutions were added separately AND at different times. The sequence was one dosage of coagulant actives, followed by four inversions of the cylinder; the second dosage of coagulant actives, four inversions; then a single dosage of flocculant (0.2 ppm 9806 as a 0.1% solution), followed by a final four inversions, after which settling rate and turbidity were determined.

These results demonstrate the effect of split addition of starch and poly(DMAEA.MCQ) solutions as coagulants in reducing turbidity. Even when added* separately, the starch and poly(DMAEA.MCQ) exhibited synergy. Adding starch as the First component followed by the addition of poly(DMAEA.MCQ) was a more effective -24program, overall, than adding the poly(DMAEA.MCQ) first. Once the prcenrage of poly(DMAEA.MCQ) was reduced to below 60% of the total actives, the turbidity from the poly(DMAEA.MCQ)-starch program rises much more rapidly than the turbidity from the starch-poly(DMIAEA.MCQ) program.

TABLEVI

R*-ulting Turbidity (NTU) of poly(DMABA.MCQ) with Starch as a Coagulant in Solution Form Effect of Order of Addition and Split Addition ~0 ~0 Treatments poly poly(DMAEA.MCQ) 2 Starch' followed by (DMAEA.MC&) Starch' Split Starch Polymer followed by Starch 3 poly(DMAEA.MCQV Split Addition Addition' 0 100 195 195 195 1468 80 74.1 77 46.1 1680 60 196 133 38.7 1724 so 342 60.8 32.9 1820 60 40 593 147 36.7 1746 80 20 968 258 29.5 1808 0 1469 1468 1 195 1469 available from Nalco Chemical Co. of Naperville, IL 3 =DRILSTAR EW (pregelatinized corn starch) available from Chemstar Products Co. of MinneapoliS.

MN

4 =percentage in first column represents dosage added first ExaMPIL The procedure described int Example I was used to obtain the results in Tables VII XIX. The results in these tables demonstrate the effect of different types of starch in the siarchlpoly(DMAEA.MCQ) blends on turbidity and settling rate of the slurry solids for 25 three different samples of slurry. The different types of-starch tested are-defined with each table.

The synergy between starch and poly(DMlAEA.MCQ) demonstrated in the previous examples is exhibited for most of the starches tested in this example- One starch that consistently performed worse than the rest was X-PAND'R which is an acidhydrolyied, pregelatinized- amylopectin and its poor performance may be due to the ~:combination of its low-molecular weight and high degree of branching. For each of the starches tested, an increase in starch content of the dry blend resulted in a two- to fourfold increase in settling rate obtained upon flocculation of the slurry solids. Thus, the addition of starch provides an enhancement in the activity of the acrylamide/acrylate flocculant, as well as an enhancement of the activity of the poly(DMAEA.MCQ) as a coagulant.

TABLE VII Resulting Turbidity (NTU) of Different Starches with poly(DMAEA.MCQ) as Dry Coagulants I Starch Type %Starch poly(DMAEA.MCQYz Starch A' Starch B* ucht 0 100 174 174 174 s0 132 98 -127 60 131 465 185 F_ 60 40 1600 3960 582 20 2500 5000 2730 2 available from Nalco Chemical Co. of Naperville, IL dextran available from Sigmta Chemical Co. of St. Louis, MO; 6 =1719 DEXTRIN (dextrin) available from Cerestar USA, Inc. of Hammond, TN 7 STALEY 620 (thinned, hydroxyethylated, instantized starch) available from A. E. Staley, of Decatur,

IL

-26- I. I. 9 9 .9 4 9 TABLE VIII Effect on Turbidity of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #1- TURBIDITY (MT) Starch Polymer poly(DADMAC)' poly(DMAEA.MCQ) Starch D' Starch E' Starch F' 0 0 100 43.5 24.7 80 51.2 56.3 34.3 60 -32.2 115 40.3 60 40 49.6 129- 44.0 1= available from Nalco Chemical Co. of Naperville, IL 2= available from Nalco chemical Co. of Naperville, IL 8= STAR-DRI 100 (maltodextrin) available from A. E. Staley (Decatur, QL 9= X-PAND'R (acid hydrolyzed, pregelatinized arnylopectin), available ftrm A. E. Staley (Decatur, IL) I1O= Pearl Starch (raw pear corn starch), avai lable from A. E. Staley (Decatur, IL) TABLE IX Effect on Settling Rate of Starch Type and Polymer:Starch Ratio in a Dry CoagulanT Slurry #1 %Starch Polymer poly(DADMAC)' poly(DMAEA.MCQ) 2 Ds E 9 Fl 0 100 4.93.3 1= available from Nalco Chemical Co. of Naperville, IL 2= available from Nalco Chemical Co. of Naperville, IL 8= STAR-DRI 100 (maltodextrin). available from A. E. Staley (Decatur, IL) X-PAND'R (acid hydrolyzed. pregelatinized amylopectin), available from A. E. Staley (Decatur, IL) I Pearl Starch (raw pearl corn starch), available ftrm A. E. Staley (Decatur, IL) .9 9 *99* 9.

9 99 9 4.

27-

TABLEX

Effect on Turbidity of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #1 TMRIDITY(N poly(DADMAC)' poly(DMAEA. Starch] Starch Starch Starch Starch Starch Polymer

MC&QG)

2 12 1 31 4 K's -0 100 29.4 28.8 s0o 34.5 48.8 56.3 50.6 33.7 60 -35.5 66.5 61.1 71.2 68.9 -40- -421s 88.7 67.6 239 94.5 =2 -vial -ro -ac -hmclC.oNprilI 2= availble from Nalco Chemical Co. of Naperville, IL I. 11 MTN-STAR 2050 (industrial grade, unmodified corn starch), available from Minnesota Corn Processors of Marshall, MN 12= STAROPOL 410 (unmodified, pregelatinized corn starch), available from A. E. Staley of Decatur, IL 13= C-GEL (instant (pregelatinized) corn starch), available from Cerestar USA Inc. of Hammond, [N 14= STARM IC 620 (blend of 2-hydroxyethyl ether starch and 2-hydroxypropyl ether hydrogen phosphate starch), available from A. E. Staley of Decatur, IL NADEX 172 (low MW cold-water soluble complex carbohydrate), available from National Starch of 15Bridgewater,

NJ

TABLEMX

2o) Effect on Settling Rate of Starch Type and Polymner:Starch Ratio in a Dry Coagulant Sluirry #l /0 ply(ADMCV CQ)Setling Rate (in/mm) poly(DMAEA. Starch IStarch Starch Starch Starch *.:Starch Polymer 2oyDDA) MC)

H'

2 I j 1

K

0 100 6.3 IM 40 5.5 3.6 4.

60 14.0 1 5.91- 10.2 9.7 4.3 4015.2 1 16.9 13.1 11.8 10.5 I =avilalefrom Nalco Chemical Co. of Naperville, IL 2= available from Nalco Chemical Co. of Naperville, IL I I MIN-STAR 2050 (industrial grade, unmodified corn starch), available from Minnesota Corn Processors of Marshall. MN 12= STAROPOL 4 10 (unmodified, pregelatinized corn starch), available from A. E. Staley of Decatur, IL 13= C-GEL (instant (pregelatiriized) corn starch). available from Ccrestar USA Inc. of Hammond, IN I14 STARMIC 620 (blend of 2-hydroxyethyl ether starch and 2-hydroxypropyl ether hydrogen phosphate starch), available from A. E. Staley of Decatur, IL I S= NADEX 772 (low MW cold-water soluble complex carbohydrate-), available from National Starch of Briditewater. NJ -28-

TABLEXI

Effect on Turbidity of Starch Type and Polymer-:Starch Ratio in a Dry Coagulant Slurry#2 TIMI!DITY (NTU) Starch Polymer poly(DADMAC)' poly(DMAEA.MCQ)a Starch Ds Starch E 9 Starch F'O 0 100 52.1 54.4 57.6 76.2 55.3 60 -473 241 64.7 40 -69.6 1564 -103 1= available from Nalco Chemical Co. of Naperville, IL 2= available from Nalco Chemical Co. of Naperville, IL 8= STAR-DR] 100'(rnaliodextrin), available from A. E. Staley (Decatur, 1L) 9= X-PAND'R (acid hydrolyzed, pregelatinized amylopectin), available from A. E. Staley (Decatur, IL) I10= Pearl Siarch (raw pearl corn starch), available from A. E. Staley (Decatur, IL) 9* 9 9 9* C. 99* 9 *999*9* *9 9 9 9.

9.

C. 9 '*9 C. .9 TABLE XIII *999 9 9* 9 C. 9 j .9.

Effect on Settling Rate of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #2 Rate (in/min) Starch Polymer poly(DADMAC)' poly(DMAEA.MCQ) 2 Starch D6 Strc E 9 Strh 0 100 10.2 9.2 80o 16.6 13.1 10.2 JO 60 -25.6 24.0 L 21.0 40 -27.2 22.8 1 23.2 I= available from Nalco Chemical Co. of Naperville, IL 2= available from Nalco Chemical Co. of Naperville. IL 8= STAR-PRI 100 (maltodextrin), available frorn A. E. Staley (Decatur, 1IL) X.PAND'R (acid hydrolyzed, pregelatinized amylopectin), available from A. E. Staley (Decatur, IQ) Pearl Starch (raw pearl corn starch), available from A. E. Sialey (Decatur, IL) 29

TABLEMXV

Effect on Turbidity of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #2 TURIDITY (TU) poly(DADMAC) -poly(DMAE&. Starch Starch Starch Starch Staidl Starch Polymer

MCQ)

2 Gil H12 1 1 0 100 118- 64 80 1 86.9 38.2 36.8 55.5 84.5 60 121 47.5 44.9 62.1 106 L 60 40 174 719 78.2 2472 89.5 -vial fro -ac -hmia -ofNprilI 2- avail1able from Nalco Chemical Co. of Naperville, IL I1= MIN~-STAR 2050 (industrial grade, unmodified corn starch), available from Minnesota Corn Processors of Marshall, WIN 12= STAR" POL 4 10 (unmodified, pregelatinized corn starch), available from A. E. Staley of Decatur, IL 13= C-GEL (instant (pregelatirtized) corn starch), available from Cerestar USA Inc. of Hammond, rN 00 14= STARMIC 620 (blend of 2-hydroxyethyl other starch anid 2-hydroxypropyl ether hydrogen phosphate starch), available from A. E. Staley of Decatur, IL I1S NADEX 772 (low MW cold-water soluble complex carbohydrate), available from Naional Starch of 1 Bridgewater, NJ 0 1* 30 TABLE XV- Effect on Settling Rate of Starch Type and Polyrner:Srarch Ratio in a Dry Coagulant Slurry #2 5_ I Settling Rate in poly(DADMA C) 'poly(DMABA. Starch Starch Starch Starch Starch Starch MCQ), G"l H'1 2 1 1 I K"s 0 22.7 3.4 90 24.5 .22.7 27.0 3S 2.

60 -24.8 36.0 32.2 29 4.2 -40 28.9 29.1 33.0 27.9 26.9 I= available from Nalco Chemical Co- of Naperville. IL 2= avai Wbe from Nalco Chemical Co. of Naperville, IL 1= MIhJ-STAR 2050 (industrial grade, unmtodified coam starch), available from Minnesota Corn Processors of Marshall, MN 10 12= STAR*POL 410 (unmodified, pregelatinized corn starch), available from A. E. Staley of Decatur, IL 13= C-GEL (instanit (pregelatinized) corn starch), available from Cerestar USA Inc. of H-ammond, IN 14= STARMvIC 620 (blend of 2-hydroxyethyl ether starch and 2-hydroxypropyl ether hydrogen phosphate starch), available from A. F_ Staley of Decatur, IL NADEX 772 (low MW cold-water soluble complex carbohydrate), available from National Starch of Bridgewater. NJ TABLE XVI Effect on Turbidity of Starch Type and Polymer,-Starch Ratio in a Dry Coagulant Slurry #3 r TURBIIITY (NT Starch Starch~ Starch Starch Polymer poly(DADMAC)' poly(DMAEA.MCQ) 2 D a 9 F' 0 1 0 100 50.1 55.9 j 20 80 63.7 57.5 .53.71 1 40 1 60 __65.8 122 64.8 1 40 -79.7 1218 1 available from Nalco Chemical Co. of Naperville, IL 2= available from Nalco Chemical Co. of Naperville, IL 8= STAR-DRI 100 (rnaltodextrin), available from A. E. Staley (Decatur, IL) 9- X-PAND'R (acid hydrolyzed, pregelatinized ataylopectin), available from A. E. Staley (Decatur, IL) I1O Pearl Starch (raw pearl corn starch), available firomn A. E. Staley (Decatur, IL) -31- TABLE XVII Effect on Settling Rate of Starch Type and Polyxner:Starch Ratio in a Dry Coagulant Slurry #3 Settling Rate (in) Starch Starch Starch Strh Plmrpl(AMClpoly(DMAEA.MCQ) 2 Do E? Flo 0 100 5.9 4. 4 4.7 4.3 12.0 0 60 140 15.0 4 13.2 40 15.8 16.6 I 15.8 6= avilbl fro Na Chmia Co. -f -aevllI 2= availAble firom Nalco Chemical Co. of Naperville, iL 8- -TR-R to 2=tdxri available from Na.c CEmia Co.le (Dcaur IaeL)e, X-PAND'R (acid hydrolyzed, pregelatintized arnylopectin), available from A. E. Staley (Decatur, IL) 1 0 10O= Pearl Starch (raw pearl corn starch), available from A. E. Staley (Decatur, IL) TABLE XVI 15Effect on Turbidity of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #3 TURBIDITY (TLT) i/ poly(DADMAC)' Poly(DMAEA. Starch Starch 'Starch Starch Starct Starch Polymer MCQ), G 1 H 12 10- i 1 Ks *0 100 48.3 60.3 0 80 43.3 56. 01 1 60-72.5 84.1 13.4 108 115 40 76.2 1237 979 691 104 Iavailable from Nalco Chemical Co. of Naperville. I L 2= available from Nalco Chemical Co. of Naperville, IL 2(I I MIN-STAR 2050 (indusrial grade, unmodified corn starch), available from Minnesota Corn Processors of Marshall, MN..

12= STAR*POL 410 (unmodified. pregelatinized corn starch), available from A. E. Staley of Decatur, IL I1' C-GEL (instant (pregelatinized) cornl starch), available from Cerestar USA Inc. of Hammnid, IN 1-1= STARMIC 620 (blend of 2-hydroxyelhyl ether starch and 2-hydroxypropyl ether hydrogen phosphate starch). available from A. E. Staley of Decatur, IL I 5m NADEX 772 (low MW cold-water soluble complex carbohydrate), available from National Starch of Bridgae'ater. NJ -32- TABLE XX Effect on Settling Rate of Starch Type and Polymer:Starch Ratio in a Dry Coagulant Slurry #3 0O SO 0* 0 0 0O 0005S0 0@ 0000 0 @0 0 S *0 0@ OS S

S.

@000 S0 OS S 5050 6S 50 0 *0S5 0 20 *500 60 0@ 0 00 S 0O 0O 1= av~table from Nalco LilemIcal UO. 01 pNdVcY'IL~.

2= available from Nalco Chemical Co. of Naperville, IL I I =MIN-STAR 2050 (industrial grade, unmodified corn starch), available from Minnesota Corn Processors of Marshall, MN 12= STAR*POL 410 (unmodified, pregelatinized corn starch), available from A. E. Staley of Decatur, IL 13= C-GEL (instant (pregelatinized) corn starch), available from Cerestar USA Inc. of Hammond, IN 14= STARMIC 620 (blend of 2-hydroyyethyI ether stach and 2-hydroxcypropyl ether hydrogen phosphate starch). available from A. E. Staley of Decatur, IL 15= NADEX 172 (low MW cold-water soluble complex carbohydrate), available from National Starch of Bridgewater, NJ Following the procedures outlined in Examples 1 and 3, and from the data put forth in Example 5, it is expected that adding dry cationic polymer and dry starch separately to the slurry system would also be an effective means to reduce turbidity. It ,would be excpected that, as dry material, the amount polymer actives would be less than that required for the same products in solution form to achieve the same level of turbidity, per Example 1. It is also expected that adding the two products separately in dry form would exhibit the same synergistic effect as that produced with the solutions.

-33 Example 7 A gravity dewatering test could be used to evaluate the efficacy of starch/cationic polymer blends for twin belt press dewatering. It is expected that starch and cationic polymers used as solutions would be particularly effective and demonstrate similar synergy in this application. The use of a starch/cationic polymer blend could also be effective in this application. -However, in the case of a dry product, it is anticipated that the cationic polymer would need to be of a low enough molecular weight and/or the dry polymer blend would need to be of a smallenough particle size so as to have the coagulant dissolve rapidly enough in the slurry system. This needs to be the case as the 0 residence time of the coagulant in the slurry system the time between the point of addition and entry into the apparatus) is much shorter for a twin belt press than for a gravity separation thickener.

Example 8 Using the same cylinder settling test and polymer preparation procedure outlined 15 in Examples 1 and 3, it is expected that the starch/cationic polymer coagulant system, both as solutions and dry product would be equally applicable, with similar anticipated results, for the settling and clarification of other mineral slurries besides coal refuse. The slurries would be of similar solids concentration and size consist as the coal refuse slurry referred to in the other examples presented here. These slurry systems could include, but -34would not be limited to, kaolin, sand and gravel, calcium phosphate dewatering, ores from precious metal processing, and iron ore.

In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprising" is used in the sense of"including", i.e. the features specified may be associated with further features in various embodiments of the invention.

It is to be understood that a reference herein to a prior art document does not constitute an admission that the document forms part of the common general knowledge in the art in Australia or any other country.

Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims: oo oo o*oo o* o *o o oo go• oo 35

Claims

1. A method for dewatering coal tailings containing water, said method comprising 2 the steps of: a. feeding said coal tailings to a thickener; 4 b. contacting said coal tailings with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; 6 c. allowing said coal tailings to settle to the bottom of the thickener to obtain concentrated coal tailings; 8 d. discharging said concentrated tailings from said thickener; and 10 e. withdrawing clarified liquid from said thickener.

2. The method according to claim 1 further comprising the addition of a flocculant.

3. The method according to claim 2 wherein said flocculant is a copolymer of 2 acrylamide and acrylic acid.

4. The method of claim I wherein the thickener is a gravity sedimentation device. S* -36- The method of claim 1 wherein said polymer is a dry polymer formed from 2 polymerization of one or more monomers selected from the group consisting of dirnethylaminoethylacrylate methyl chloride quaternary salt, acrylaznide, 4 dimethylaminoethylacrylate benzyl chloride quaternary salt, dimethylaiioethylmethacrylate methyl chloride quaternary salt- 6 dimethylaminoethylmethyacrylate benzyl chloride quaternary salt diallyldimethylanxnoniurfl chloride and combinations thereof. The method of claim 1 wherein said polymer is a solution polymer formed from 2 polymerization of one or more monomers selected from the group consisting of dimethylaminoeihylacrylaie methyl chloride quaternary salt, dimethylaminoethylacrylate 4 bcnzyl chloride quaternary salt, dimethylamninoethYlmnethacrylate methyl chloride quaternary salt, dimethylaxninoethylmethyacrylate benzyl chloride quaternary salt, 6 diallyidi methylammonium chloride and combinations thereof, The method of claim I wherein said starch is selected from the group consisting 2ocf unmodified starch, pregelatinized starch, hydrolyzed starch and combinations thereof.

8. The method of claim I wherein said combination is at least 30 weight percent 2starch.

9. The method of claim I wherein said polymer is poly(diinethylaminoethylacrylate 2 methyl chloride quaternary salt) and said starch is unmodified starch. -37. The method of claim 9 wherein the ratio of polymer to starch in said -ombination 2 is from about 70:30 to about 20:80.

11. The method of claim 9 wherein the ratio of polymer to stach in said combination 2 is from about 60:40 to about 25:75.

12. The method of claim 9 wherein the ratio of polymer to starch in said combination 2 is from about 50:50 to about 35:65.

13. A method for dewatering a clean coal product containing water comprising the 2 steps of: a. feeding a clean coal product containing water to a mechanical filtering 4 device; b. contacting said clean coal product with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; c. removing water from said clean coal product; and then, d. recovering a dewatered clean coal product from the mechanical filtering device.

14. The method according to claim 13 further comprising the addition of a flocculant. The method according to claim 14 wherein said flocculant is a copolymer of 2 acrylamide and acrylic acid. -38-

16. The method of claim 13 wherein said polymer is a dry polymer formed from 2 polymerization of one or more monomers selected from the group consisting o2f dimethylaminoethylacrylate methyl chloride quaternary salt, acrylamide, 4 dimethylaminoethylacrylate benzyl chloride quaternary salt, dimethylaminoethylznethacrylate methyl chloride quaternary salt- 6 dirnethylamninoethylmethyacrylate benzyl chloride quaternary salt, diallyldimethylnhmoium chloride and combinations thereof. .17. The method of claim 13 wherein said polymer is a solution polymer formed from 2the polymerization of one or more monomers selected from the group consisting of dimethylaminoethylacrylate methyl chloride quaternary salt, dimethylamninoethylacrylate 4 benzyvl Chloride quaternary salt, dimethylaminoethylmnethacrylate methyl chloride quaternary salt, dimethylaminoethylmethyaclylate benzyl chloride quaternary salt, 6 diallvldiniethylammonium chloride and combinations thereof. 18,S The method of claim 13 wherein said starch is selected from the group consisting 2 of unmiodified starch, pregelatinized starch, hydrolyzed starch and combinations thereof.

19. The method of claim 13 wherein said combination is at least 30 weight percent 2 starch- The mcthod of claim 13 wherein said polymer is poly(djmethylaminoethylacly late 2 methyl chloride quaternary salt) and said starch is unmodified starch. -39-

21. The method of claim 20 wherein the ratio of polymer to starch in saidL.. 2 combination is from about 70 :30 to about 20:80.

22. The method of claim 20 wherein the ratio of polymer to starch in said 2 combination is from about 60:40 to about 25:75.

23. The method of claim 20 wherein the ratio of polymer to starch in said 2 combination is from about 50:50 to about 35:65.

24. The method of claim 13 wherein said mechanical filtering device is selected from 2 the group consisting of gravity thickeners, twin belt presses and rotary drum filters. A method for dewatering mineral slurries containing water comprising the steps a. feeding the mineral slurry into a thickener; b. treating said mineral slurry with an effective coagulating amount of a coagulant comprising a combination of a cationic polymer and a starch; 6 c. allowing the water to separate from the mineral slurry; d. withdrawing water from said thickener; and e. discharging the dewatered mineral products from said thickener.

26. The method of claim 25 wherein the mineral slurry is selected from the group consisting of: titania. copper, trona. beryllium and taconite slurries. 27, The method of claim 25 further comprising the addition of a flocculant.

28. The method of claim 27. wherein said flocculant is a copolymer of acrylamide and 2 acrylic acid.

29. The method of claim 25 wherein said polymer is a dry polymer is formed from 2 polymerization bf one or more mnomers selected from the group consisting of di methylairinoethylacrylate methyl chloride quatemary salt, acrylamide, V'06, 4 dirnethylaminoethylacrylate benzyl chloride quaternary salt, di methylaminoethylmethacrylate methyl chloride quaternary salt, 6 dimnethyvlaminoethylmethyacrylate benzyl chloride quaternary salt, diallyldirnethylarnofiurn chloride and combinations thereof. The method of claim 25 wherein said polymer is a solution formed from 2polymerization of one or more monomers selected from the group consisting of di methvlami noethylacrylate methyl chloride quaternary salt, dirnethylaminoethylacrylate ibenz0 chloride quaternary salt. dirnethylaxninoethylrnethacrylate methyl chloride quaternary -salt. dimethylaminaethyImethyacrylIate benzyl chloride quaternary salt, 6 diallyldimethylamrnonium chloride and combinations thereof. I1 The method of claim 25 wherein said starch is selected from the group consisting 2 ol unrnodified starch. pregelatinized starch, hydrolyzed starch and combinations thereof. 41

32. The method of claim 25 wherein said combination is at least 30 weight percent 2 starch.

33. The method of claim 25 wherein said polymer is poly(dimethylaminoethylacrylate 2 methyl chloride quaternary salt) and said starch is unmodified starch.

34. The method of claim 33_wherein the ratio of polymer to starch in said 2 combination is from about 70 :30 to about 20:80. The method of claim 33 wherein the ratio of polymer to starch in said combination is from about 60:40 to about 25:75.

36. The method of claim 33 wherein the ratio of polymer to starch in said 2 combination is from about 50:50 to about 35:65.

37. A method for clarifying the water contained in a coal refuse slurry, said method Scolmprising the steps of: a. treating the coal refuse slurry with an effective coagulating amount of a 4 coagulant comprising a combination of a cationic polymer and a starch; b. allowing the water to separate from the coal refuse; 6 c. feeding the separated water and coal refuse into a twin belt filter press; d. withdrawing the clarified water through the twirn belt filter press; and 8 e. removing the coal refuse from the twin belt filter press. -42- 38 The method according to claim 37 further comprising the addition of -flocculant.

39. The method according to claim 37 wherein said flocculant is a copolymer of 2 acrylamide and acrylic acid. The method of claim 37 wherein said polymer is a dry polymer is formed from 2 polymerization of one or more monomers selected from the group consisting of dimethylaminoethylacrylate methyl chloride quaternary salt, acrylamnide, *4 dimethylaminoethylacrylate benzyl chloride quaternary salt, dimethylam inoethylmethacrylate methyl chloride quaternary salt, 6 dimethylamninoethylmethyacryla~te benzyl chloride quaternary salt, dial lyldirnethylarnmonium chloride and combinations thereof

41. The method of cilaim 37 wherein said polymner is a solution polymer formed from 2 polymierization of one or more monomers selected from the group consisting of di methv laminoethylacrylate methyl chloride quaternary salt, dimethylaminoethylacrylate 4 hcnz-vl chloride quaternary salt. dimethylaminoethylmethacrylate methyl chloride quaternary salt, dimethylaminoethylmethyacrylate bcnzyl chloride quatenary salt,- 6 diallyldimerhylammonium chloride and combinations thereof.

42. The method of claim 37 wherein said starch is selected from the group consisting 2 of unmnodified starch, pregelatinized starch, hydrolyzed starch and combinations thereof. -43-

43. 2 starch. The method of claim 37 wherein said combination is at least 30 weight percent 9 .9 C.

44. The method of claim 37 wherein said polymer is poly(dimethylaminoethylacrylate 2 methyl chloride quaternary salt) and said starch is unmodified.- The method-of claim 44. wherein the ratio of polymer to starch in said 2 combination is from about 70 :30 to about 20:80.

46. The method of claim 44 wherein the ratio of polymer to starch in said 2 combination is from about 60:40 to about 25:75.

47. The method of claim 44 wherein the ratio of polymer to starch in said 2 combination is from about 50:50 to about 35:65. -44 i

48. A method for dewatering coal tailings containing water, said method substantially as herein described with reference to the examples.

49. A method for dewatering clean coal product containing water,_said method substantially as herein described with reference to the examples.

50. A method for dewatering mineral slurries containing water, said method substantially as herein described with reference to the examples.

51. A method for clarifying the water contained in a coal refuse slurry, said method substantially as 6 herein described with reference to the examples. 0 Dated this 29th day of September 1998 NALCO CHEMICAL COMPANY By their Patent Attorneys GRIFFITH HACK